Synfacts 2007(5): 0510-0510  
DOI: 10.1055/s-2007-968462
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Dynamic Kinetic Resolution of Aldehydes via Hydrogenation with Ruthenium

Contributor(s):Hisashi Yamamoto, Joshua N. Payette
J.-H. Xie, Z.-T. Zhou, W.-L. Kong, Q.-L. Zhou*
Nankai University, Tianjin, P. R. of China
Rh-Catalyzed Asymmetric Hydrogenation of Racemic Aldehydes via Dynamic Kinetic Resolution: Efficient Synthesis of Optically Active Primary Alcohols
J. Am. Chem. Soc.  2007,  129:  1868-1869  
Further Information

Publication History

Publication Date:
24 April 2007 (online)


Significance

While chiral secondary alcohols are easily obtained from hydrogenation of the corresponding prochiral ketone, few methods for the synthesis of chiral primary alcohols exist by asymmetric hydrogenation. In this study, these substrates are obtained by the asymmetric hydrogenation of racemic α-branched aldehydes via dynamic kinetic resolution (DKR). An example of the utility of this system is demonstrated in the short synthesis of a biologically active compound.

Comment

The authors indicate that a bulky alkyl group at the α-position of the racemic aldehyde is essential for obtaining high asymmetric induction. Also, the position and electronic properties of substituents on the aryl ring seem to have little effect on enantioselectivites. Deuteration studies indicate that hydrogenation via DKR occurs at the carbonyl group rather than at the enol form of the aldehyde.